The multiple coupling of composite laminates has a unique advantage in improving the macro mechanical properties of composite structures. A total of three hygro-thermally stable multi-coupled laminates with extensiontwisting coupling were presented, which were conducive to the formation of passive adaptive structures. Then, the multi-coupled laminates were used to design the bending-twisting coupled box structure, in which the configuration of laminate and box structure could be extended to variable cross-section configuration. The optimal design of stacking sequence was realized, the optimization objectives of which were to maximize bending-twisting coupling of box structure and extension-twisting coupling of laminate, respectively. The effects of multiple coupling on hygro-thermal stability, coupling, failure strength, buckling load, robustness and other comprehensive mechanical properties of laminates and box structures were analyzed by parametric modeling method. The results show that the extension-twisting coupling of laminate and the bending-twisting coupling of box structures can be greatly improved by 450% and 260% at maximum, respectively. Meanwhile, it would have a negative impact on the failure strength and buckling load, which, however, can be minimized by a reasonable paving method. Multicoupled laminates have good robustness, and the bending-twisting coupling helps improve robustness. Finally, the hygro-thermal stability and mechanical properties were verified by numerical simulation with finite element method.